EP0565690B1 - Dispositif a tuyere pour l'introduction de milieux dans une masse en fusion et procede pour la mise uvre de ce dispositif - Google Patents

Dispositif a tuyere pour l'introduction de milieux dans une masse en fusion et procede pour la mise uvre de ce dispositif Download PDF

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Publication number
EP0565690B1
EP0565690B1 EP92922854A EP92922854A EP0565690B1 EP 0565690 B1 EP0565690 B1 EP 0565690B1 EP 92922854 A EP92922854 A EP 92922854A EP 92922854 A EP92922854 A EP 92922854A EP 0565690 B1 EP0565690 B1 EP 0565690B1
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EP
European Patent Office
Prior art keywords
nozzle
sleeve
assembly according
nozzle assembly
tube
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92922854A
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German (de)
English (en)
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EP0565690A1 (fr
Inventor
William Wells
Georg Raidl
Walter Schmelzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kortec AG
Original Assignee
Mannesmann AG
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Filing date
Publication date
Application filed by Mannesmann AG filed Critical Mannesmann AG
Publication of EP0565690A1 publication Critical patent/EP0565690A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
    • B22D1/002—Treatment with gases
    • B22D1/005—Injection assemblies therefor
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/42—Constructional features of converters
    • C21C5/46—Details or accessories
    • C21C5/48—Bottoms or tuyéres of converters

Definitions

  • the invention relates to a nozzle device for introducing media into a melt according to the preamble of claim 1. Furthermore, it relates to a method for operating this nozzle device.
  • a nozzle device of this type has become known from DE-C2-38 09 828.
  • the known device for introducing gases and / or solid reaction substances and additives into a metallurgical melting vessel contains a perforated brick inserted into the wall of the melting vessel which axially displaceably receives a flushing brick which has at least one gas duct which can be connected to a gas line.
  • the outlet opening of the gas channel is provided on the circumferential surface of the sink block so that it is only released and the media can be introduced into the melt when the sink block is advanced with its inner end over the annular end face of the perforated block.
  • the nozzle device By pulling back the purging plug, a closure is ensured without the need to apply a continuous gas pressure to the purging system, so that the nozzle device is particularly suitable for transport vessels, such as a pan, in which it is not possible to use the gas purging system over the entire residence time of the melt to supply gas in the vessel.
  • the axial displacement of the flushing stone thus serves the task of being able to use it not only for introducing media but also as a closure member.
  • a nozzle for introducing fresh gas, in particular oxygen, has become known through the wall of a fresh vessel below the bath surface, in which the fresh gas is passed through an inner tube and through a concentric one
  • a protective medium can be passed into the outer tube into the melt and the two tubes are arranged concentrically in a stationary jacket tube.
  • the inner and outer tubes are axially displaceable and interchangeable, each spaced in at least one jacket tube.
  • At least one additional annular space is created for introducing a protective medium, and there is the possibility of changing the inner and outer tubes between two batches or moving them axially to influence the masonry wear in the immediate vicinity of the nozzles.
  • the inner and outer tubes can be advanced and the funnel can then be filled, for example by spraying or tamping.
  • EP-B1-0 182 965 discloses a method for protecting a nozzle from at least three concentric tubes, through which a central channel and at least two ring channels are formed, in which an oxygen-containing gas and an annular channel pass through the central channel a mist of atomized water is blown in as the cooling fluid, the atomization of the water being carried out by means of a carrier gas in a nozzle head on the inlet side of the nozzle.
  • This cooling fluid has proven to be particularly effective in increasing the service life of the nozzle.
  • GB-A-2 140 142 discloses a gas purging arrangement with a metallic or ceramic tube which is axially displaceable within a perforated brick.
  • the tube can consist of several tube sections screwed or otherwise connected and contain gas-permeable inserts which are firmly inserted into the tube and are axially displaceable together with it.
  • the outer surface of the tube is preferably covered with a refractory lubricant layer, for example made of graphite.
  • the metallic or ceramic tube including the inserts, is pushed into the interior of the furnace, refractory mass 19 stamped and then put the nozzle device back into operation.
  • the uppermost tip of the nozzle which is closed by solidified metal, is washed away when the new melt is introduced and the nozzle arrangement is brought into its functional state.
  • US-A-3,829,073 describes a nozzle device with two spaced apart concentric tubes, the outer of which is embedded in a filling material made of refractory material, which is stamped between the outer tube and a tubular casing.
  • a filling material made of refractory material, which is stamped between the outer tube and a tubular casing.
  • the ramming mass is subjected to an overpressure from the outside.
  • GB-A-1 152 330 discloses a nozzle device with two concentric steel tubes spaced apart.
  • a reactive gas, such as oxygen, is optionally mixed with an inert gas through the central channel and an inert gas is introduced through the ring channel between the two concentric tubes to protect the nozzle tip.
  • the outer of the two concentric pipes is cemented into a perforated brick using a filling material made of refractory material.
  • the gas flows introduced through the nozzle are switched off.
  • the metal melt penetrating into the nozzle tip solidifies inside the nozzle and the latter is replaced by a new nozzle after the liquid metal has been tapped from the vessel.
  • US-A-4,449,701 describes a non-displaceable nozzle device projecting over the inner wall of the furnace, for blowing in a non-oxidizing gas, from two concentrically spaced pipes, the inner pipe being filled with refractory material and through the annular gap between the inside - and the Outer tube gases are introduced.
  • the distance between the inner and the outer tube is determined by suitable helically arranged spacers.
  • the object of the invention is to increase the service life in a nozzle device for introducing media into a melt, to shorten the downtimes and to simplify the maintenance work. Furthermore, a method for operating this nozzle device is to be specified.
  • the nozzle device according to the invention is characterized by the features of claim 1, the method according to the invention by the features of claim 11.
  • both the consuming tip of the nozzle tubes and the refractory material surrounding this tip are replaced either continuously or periodically by re-inserting the sleeve containing the metallic nozzle tube or the metallic nozzle tubes. Since the nozzle is intended for use below the bath level of the melt, in addition to the axial displaceability of the sleeve, it must also be ensured that no melt can penetrate into the annular gap between the surfaces to be displaced relative to one another. This is made possible by covering the sleeve with a thermally resilient lubricant layer, providing an annular gap between the outside of the sleeve and the inside of the perforated brick and sealing it with a cement layer.
  • the sleeve protrudes a substantial amount on the outside of the perforated brick.
  • Pushing the sleeve receiving the metallic nozzle tube together with the nozzle tube has problems, namely damage to the sleeve, because of the different bending elasticity of metal and ceramic when the sleeve is subjected to buckling loads. It has been shown that the difficulties can be overcome if the metallic nozzle tube is not inserted firmly into the bore of the sleeve but is axially displaceable.
  • the outside of the nozzle tube adjacent to the inside of the sleeve is covered with a thermally resilient lubricant layer, an annular gap is provided between this outside of the nozzle tube and the inside of the sleeve and this is sealed with a cement layer.
  • the cement layer for sealing the respective annular gap after the sleeve has been introduced into the perforated brick or the nozzle tube pressed into the sleeve are provided in the perforated brick or in the sleeve approximately in the middle of their axial length.
  • the service life of the nozzle device can already be significantly increased by the continuous or periodic replacement of the nozzle tip, a further increase in the service life is possible if, in addition to the treatment media, such as oxygen, coal dust etc., a cooling fluid is also introduced. In this case, the lowering of the temperature along the sliding surfaces between the perforated brick and the sleeve or sleeve and the outer nozzle tube also maintains the mutual displaceability for longer.
  • the treatment media such as oxygen, coal dust etc.
  • the cooling fluid can be introduced, for example blown in, together with the treatment agent.
  • a nozzle device in which at least two concentric, metallic nozzle pipes are inserted into the sleeve, which form a central channel and at least one ring channel surrounding the central channel, the treatment agent and then through a channel another channel the cooling fluid is introduced.
  • a particularly effective cooling is achieved if a mist of atomized water is supplied as cooling fluid to a channel, in particular the outer ring channel.
  • the sleeve protrude from the perforated brick into the melt by a certain protrusion, for example in the order of magnitude of 100 mm.
  • the desired projection can be maintained by pushing the sleeve.
  • the nozzle device can be used with different melts, in particular such as metal melts, iron melts and lead melts. Due to its dimensions, it can also be adapted to the media to be introduced, which can be gaseous, liquid, pasty or dusty.
  • the nozzle device shown in FIGS. 1 and 2 contains a perforated brick 3 made of refractory material that can be inserted into the wall 1 of a vessel 2.
  • the wall of the vessel can be the bottom wall or the side wall of the vessel.
  • the perforated brick is to be used in such a way that the medium introduced through the nozzle device is fed to the melt below the bath level.
  • the perforated brick 3 axially slidably receives a sleeve 4 made of a refractory mass, which has an axial bore 5.
  • a sleeve 4 made of a refractory mass, which has an axial bore 5.
  • two concentric metallic nozzle tubes 6 and 7 are inserted at a distance from one another, which form a central channel 8 and an annular channel 9 surrounding the central channel. These channels are connected at the outer end of the nozzle tubes with connections 10 and 11 for the media to be introduced.
  • the sleeve 4 including the nozzle tubes 6 and 7, with its nozzle tip pointing into the interior of the vessel, that is to say with its inner end, protrudes beyond the inner end face 12 of the perforated brick 3, extends through the perforated brick 3 and stands with its outer End by a substantial amount, which in the case shown corresponds approximately to the length of the perforated brick from the outer end face 13 of the perforated brick 3.
  • the outer end of the sleeve 4 is provided with a first pressure plate 14 which is guided by guide rods 15 fastened to the housing wall and running parallel to the sleeve 4.
  • 16 with a flange is designated which carries the guide rods 15 and on the outer steel jacket 17 of the furnace vessel 2 is attached.
  • the flange 16 also carries a sealing device 18.
  • the outer ends of the concentric nozzle tubes 6 and 7 are fastened in a nozzle head 19, which has a second pressure plate 20 on its outer end face, which is non-positively connected to the first pressure plate 14. This second pressure plate 20 is also guided by the guide rods 15.
  • the sleeve 4 is coated with a lubricant layer 21 and an annular gap between the outside of the sleeve 4 and the inside of the perforated brick 3 is sealed with a cement layer 22.
  • the lubricant layer 21 is applied before the sleeve 4 is inserted into the perforated brick 3.
  • This can be, for example, a cover layer made of sliding material, such as a molybdenum compound, firmly attached to the sleeve 4.
  • the sliding layer can also be applied to the sleeve 4 in the form of a film immediately before it is inserted.
  • a radial bore 23 is provided in the perforated brick 3, through which the cement layer is pressed.
  • the thickness of the annular gap that is to be filled by the sealing cement layer must be chosen so that the layer pressed in via the radial bore 23 can penetrate to the end faces 12 and 13 of the perforated brick. With the usual dimensions, a value of 0.5 to 1 mm has proven to be expedient as the thickness for the annular gap to be filled through the cement layer.
  • the inner nozzle tube 7 is held at a distance within the outer nozzle tube 6 by spacers, not shown, to form the annular channel 9. It must be ensured that the spacers do not significantly impair the media flow through the ring channel 9.
  • the outer tube 6 is inserted into the sleeve 4 so that, on the one hand, there is a tight seal between the outside of the outer tube and the inside of the sleeve, but on the other hand slight longitudinal displacements between the sleeve and the outer tube are possible, i.e. the transmission of axial forces at the interface between the sleeve and the outer tube is largely avoided.
  • a lubricant layer 25 is applied to the outer tube 6 - this can be a solid coating applied during the manufacture of the tube or a coating applied before the tube is inserted - and it becomes at least after the tubes 6 and 7 have been inserted a provided in the sleeve 4 radial bore 26, a cement layer 27 for sealing an annular gap between the outer tube 6 and sleeve 4 is pressed.
  • a magnesite-phosphate compound is preferably used for the treatment of an iron melt
  • a magnesite-chromium compound is preferably used for the treatment of a lead melt
  • a magnesite-silicon compound is preferably used for the treatment of a glass melt.
  • a line for the supply of oxygen gas or pulverized coal suspended in a carrier gas is connected to the connection 10 which is connected to the central channel 8 of the inner nozzle tube 7 and a line for the supply of a cooling fluid, preferably a mist of atomized water, to the connection 11 connected to the ring channel 9.
  • a cooling fluid preferably a mist of atomized water
  • the water can also be atomized by means of an atomizing device provided in the nozzle head 19, as described, for example, in EP-182 965.
  • the nozzle device shown only partially in FIGS. 3 and 4 contains a conical perforated brick 3 and only one nozzle tube 6.
  • the same reference symbols have been chosen. Reference is made to the description of these parts relating to the first exemplary embodiment.
  • the nozzle device according to the second exemplary embodiment has been used for the oxidation of lead ores and for the reduction of lead oxide slag in order to form metallic lead.
  • the treatment process is divided into two sections, namely an oxidation section and a reduction section.
  • the oxidation section produces slags with a high iron oxide and lead oxide content.
  • the working temperature is between 1000 and 1100 ° C. This is the section with the higher nozzle wear.
  • the slag In the reduction section there are operating temperatures between 1200 and 1300 ° C, the slag has a low lead oxide content, namely about 2% and contains about 20% iron oxide.
  • chrome magnesite is used both for the consecutive perforated brick 3 and for the sleeve 4.
  • the treatment agent is introduced through the central channel of the nozzle tube 6.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Furnace Charging Or Discharging (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)
  • Nozzles (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
  • Continuous Casting (AREA)
  • Gasification And Melting Of Waste (AREA)
  • Glanulating (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Blast Furnaces (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Manufacture Of Iron (AREA)

Claims (14)

  1. Dispositif à buse pour introduire des fluides dans un bain de fusion, comportant une brique creuse (3) en une matière réfractaire, pouvant être mise en place dans la paroi (1) d'un récipient (2), laquelle reçoit de façon axialement mobile un corps cylindrique en une masse réfractaire ayant un perçage axial (5) pour l'introduction du gaz ou du fluide de traitement, lequel corps, relativement à l'extrémité de la buse orientée, dans l'état monté, vers l'intérieur du récipient, fait saillie de la brique creuse (3) par son extrémité externe opposée et est muni, à cette extrémité, d'une première plaque de pression (14) pour le déplacement axial du corps, avec la caractéristique que le corps cylindrique est réalisé sous forme de manchon (4) dans lequel sont mis en place au moins deux tubes de buse métalliques concentriques (6,7), qui forment un canal central (8) et au moins un canal annulaire (9) entourant le canal central, et que ces canaux sont reliés, à l'extrémité externe des tubes de buse, à des raccords (10,11) pour les fluides à introduire.
  2. Dispositif à buse selon la revendication 1,
    caractérisé en ce que le manchon (4) est revêtu d'une couche de lubrifiant (21) pouvant être thermiquement chargée, et une fente annulaire entre la face externe du manchon (4) et la face interne de la brique creuse (3) est étanchéifiée par une couche de ciment (22).
  3. Dispositif à buse selon une des revendications 1 à 2,
    caractérisé en ce que le manchon (4) présente des nervures longitudinales s'étendant axialement sur sa face externe, lesquelles sont réparties sur la périphérie du manchon.
  4. Dispositif à buse selon une des revendications 1 à 3,
    caractérisé en ce que la face externe, voisine de la face interne du manchon (4), du tube de buse (6) est revêtue d'une couche de lubrifiant (25) pouvant être chargée thermiquement, et une fente annulaire entre la face externe du tube de buse (6) et la face interne du manchon (4) est étanchéifiée par une couche de ciment (27).
  5. Dispositif à buse selon une des revendications 1 à 4,
    caractérisé en ce que la brique creuse (3) et/ou le manchon (4) présentent, à peu près au centre de leur longueur axiale, un perçage radial (23 ou 26) pour l'injection de ciment.
  6. Dispositif à buse selon une des revendications 1 à 5,
    caractérisé en ce que l'extrémité externe du tube de buse (6) ou les extrémités externes des tubes de buse (6,7) sont fixées dans une tête de buse (19) qui présente, sur la face frontale externe, une seconde plaque de pression (20) qui est reliée, sous l'influence d'une force, à la première plaque de pression (14).
  7. Dispositif à buse selon une des revendications 1 à 6,
    caractérisé en ce que la ou les plaques de pression (14,20) sont guidées par des barres de guidage (15) fixées à la paroi de bâti et s'étendant parallèlement au manchon.
  8. Dispositif à buse selon une des revendications 1 à 7,
    caractérisé en ce que la matière réfractaire de la brique creuse (3) et/ou du manchon (4) est constituée essentiellement de magnésite ou de magnésite-chrome.
  9. Dispositif à buse selon une des revendications 1 à 8,
    caractérisé en ce que la couche de lubrifiant (21,25) est constituée essentiellement d'une pâte de graphite, d'un composé de molybdène, de stéatite ou de suif.
  10. Dispositif à buse selon une des revendications 1 à 9,
    caractérisé en ce que la couche de ciment (22,27) est constituée essentiellement d'un composé magnésite-phosphate, magnésite-chrome, ou magnésite-silicium.
  11. Procédé pour mettre en oeuvre un dispositif à buse selon une des revendications 1 à 10, lequel est monté dans la paroi (1) d'un récipient (21) recevant un bain de fusion et à travers lequel des fluides sont introduits au-dessous de la surface du bain de fusion,
    caractérisé en ce que l'extrémité de buse consommée est remplacée de façon continue ou à des intervalles de temps par poussée du manchon (4) à l'intérieur du récipient en même temps que le ou les tubes de buse (6,7).
  12. Procédé selon la revendication 11,
    caractérisé en ce qu'une saillie (a) au-delà de la face frontale interne (12) de la brique creuse (3) est toujours conservée par poussée du manchon.
  13. Procédé selon la revendication 11 ou 12,
    caractérisé en ce qu'un fluide de refroidissement est introduit à travers un des canaux (9), en particulier le canal annulaire externe.
  14. Procédé selon la revendication 13,
    caractérisé en ce qu'un nuage d'eau pulvérisée est amené au canal (9) comme fluide de refroidissement.
EP92922854A 1991-11-06 1992-11-03 Dispositif a tuyere pour l'introduction de milieux dans une masse en fusion et procede pour la mise uvre de ce dispositif Expired - Lifetime EP0565690B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4136552 1991-11-06
DE4136552A DE4136552A1 (de) 1991-11-06 1991-11-06 Dueseneinrichtung zum einleiten von medien in eine schmelze und verfahren zum betrieb dieser dueseneinrichtung
PCT/EP1992/002520 WO1993009255A1 (fr) 1991-11-06 1992-11-03 Dispositif a tuyere pour l'introduction de milieux dans une masse en fusion et procede pour la mise ×uvre de ce dispositif

Publications (2)

Publication Number Publication Date
EP0565690A1 EP0565690A1 (fr) 1993-10-20
EP0565690B1 true EP0565690B1 (fr) 1997-03-05

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EP92922854A Expired - Lifetime EP0565690B1 (fr) 1991-11-06 1992-11-03 Dispositif a tuyere pour l'introduction de milieux dans une masse en fusion et procede pour la mise uvre de ce dispositif

Country Status (16)

Country Link
US (1) US5465942A (fr)
EP (1) EP0565690B1 (fr)
JP (1) JPH0781790B2 (fr)
KR (1) KR100206639B1 (fr)
CN (1) CN1027596C (fr)
AT (1) ATE149574T1 (fr)
AU (1) AU659242B2 (fr)
BR (1) BR9205420A (fr)
CA (1) CA2099781C (fr)
DE (2) DE4136552A1 (fr)
ES (1) ES2098551T3 (fr)
RU (1) RU2080393C1 (fr)
TR (1) TR27311A (fr)
UA (1) UA32416C2 (fr)
WO (1) WO1993009255A1 (fr)
ZA (1) ZA928448B (fr)

Cited By (2)

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WO2008153440A2 (fr) 2007-04-26 2008-12-18 Techkom Gmbh Dispositif à tuyère destiné à l'injection de milieux gazeux sous un niveau de métal en fusion
MD3946G2 (ro) * 2003-06-16 2010-02-28 Techcom Import Export Gmbh Dispozitiv al gurii de vânt pentru introducerea mediilor gazoase sub un strat de metal lichid

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DE10328420B3 (de) * 2003-06-25 2004-08-26 Rhi Ag Düseneinrichtung und deren Verwendung in einem metallurgischen Schmelzgefäß
DE10347947B4 (de) * 2003-10-15 2007-04-12 Maerz-Gautschi Industrieofenanlagen Gmbh Industrieofen und zugehöriges Düsenelement
RU2471874C1 (ru) * 2011-12-19 2013-01-10 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" Способ удаления титана из высокохромистых расплавов
KR101447581B1 (ko) * 2013-11-25 2014-10-07 국도정밀(주) 제련로용 인젝션 노즐 인입장치
DE102013114080A1 (de) * 2013-12-16 2015-06-18 Norma Germany Gmbh Element einer Schellen-Flansch-Verbindung
WO2019014914A1 (fr) * 2017-07-21 2019-01-24 Linde Ag Agencement de buse pour la fusion d'un matériau en poudre
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JPH01208411A (ja) * 1988-02-16 1989-08-22 Nippon Steel Corp 溶融金属炉のガスノズルの冷却法
DE3809828A1 (de) * 1988-03-23 1989-10-12 Radex Heraklith Spuelstein
DE3907887A1 (de) * 1988-03-23 1989-10-26 Radex Heraklith Spuelstein
DE3833502A1 (de) * 1988-10-01 1990-04-05 Didier Werke Ag Gasspuelstein
DE3904356A1 (de) * 1989-02-14 1990-08-23 Didier Werke Ag Gasspueleinrichtung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD3946G2 (ro) * 2003-06-16 2010-02-28 Techcom Import Export Gmbh Dispozitiv al gurii de vânt pentru introducerea mediilor gazoase sub un strat de metal lichid
WO2008153440A2 (fr) 2007-04-26 2008-12-18 Techkom Gmbh Dispositif à tuyère destiné à l'injection de milieux gazeux sous un niveau de métal en fusion

Also Published As

Publication number Publication date
CN1074485A (zh) 1993-07-21
KR100206639B1 (ko) 1999-07-01
CA2099781A1 (fr) 1993-05-07
ATE149574T1 (de) 1997-03-15
WO1993009255A1 (fr) 1993-05-13
DE59208130D1 (de) 1997-04-10
DE4136552A1 (de) 1993-05-13
EP0565690A1 (fr) 1993-10-20
CN1027596C (zh) 1995-02-08
TR27311A (tr) 1995-01-10
ES2098551T3 (es) 1997-05-01
BR9205420A (pt) 1993-11-23
JPH06500162A (ja) 1994-01-06
UA32416C2 (uk) 2000-12-15
AU2894892A (en) 1993-06-07
JPH0781790B2 (ja) 1995-09-06
CA2099781C (fr) 1998-08-04
AU659242B2 (en) 1995-05-11
US5465942A (en) 1995-11-14
ZA928448B (en) 1993-05-05
RU2080393C1 (ru) 1997-05-27
KR930703469A (ko) 1993-11-30

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